Latest ArticlesYnones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis, thus great efforts have been devoted to their preparation. While, introducing prochiral substrates to construct ynones bearing a chiral framework is unrealized to date. Herein, we reported the first example of Pd/SOP-catalyzed asymmetric carbonylative alkynylation via a non-classical carbonylative Sonogashira-type approach (acyl-Pd(Ⅱ) species generated from nucleophiles). By using cyclic diaryliodonium salts as prochiral substrates, various axial chiral ynones with good functional group tolerance (39 examples), satisfied yields (71%-96%) and excellent enantioselectivities (generally 94%-99% ee) were produced. Synthesis of bioactive compounds, scale-up experiment and useful transformations were also conducted to demonstrate the utility of this process.
Macrocycle confinement induced guest near-infrared (NIR) luminescence was research hotspot currently. Here in, we reported a cucurbit[7]uril (CB[7]) confined 3,7-bis((E)-2-(pyridin-4-yl)vinyl)-10-H-phenothiazine bridged bis(4-(4-bromophenyl)pyridine) (G), which not only boosted its NIR luminescence but also realized detection of HClO/ClO− in living cells and lysosome imaging. Fluorescence spectroscopy experiments were performed to calculate the detection ability of probe G to HClO/ClO− up to 147 nmol/L. As compared with G, supramolecular probe G⊂CB[7] formed after encapsulated by CB[7], the detection ability towards HClO/ClO− was improved to 24 nmol/L which was ascribe to the macrocycle CB[7] confinement increasing the fluorescence intensity to 103 folds. Accompanying the excitation wavelength changing, the fluorescence red-shifted to 820 nm when excited by 570 nm light, which was used to NIR lysosome imaging. Meanwhile, the supramolecular assembly G⊂CB[7] was also successfully used to highly sense to exogenous HClO/ClO− in RAW 264.7 cells and live animal.
The seven-membered ring motifs are found in bioactive pharmaceuticals and a wide range of natural products, including alkaloids and terpenoids, which hold significant importance in synthetic chemistry and has garnered considerable attention from both academia and industry. Despite the challenges faced in the past decade, the total synthesis of natural products incorporating the non-aromatic cycloheptane skeletons remains a compelling pursuit. Recently, numerous elegant strategies for constructing the seven-membered ring system have been successfully developed. This review focuses on the recent advancements in this field from 2017 to April 2023, highlighting key transformations utilized to construct the non-aromatic cycloheptane core structures and serves as a valuable guide for synthetic chemists engaged in the total synthesis of natural products containing seven-membered ring motifs.
We report the unprecedent Pd(I) catalyzed ring-opening arylation of cyclopropyl-α-aminoamides. This protocol allows facile access to biologically important α-ketoamide-containing oligopeptides and even more challenging peptide-natural product conjugates. Site selectivity was achieved by introduction of special unnatural amino acids, which also meets the requisite of bioorthogonal chemistry. Mechanism investigations reveals a distinct domino radical ring-opening process through Pd(I) catalysis.
The classification of π-/σ-aromaticity depends on the electrons with the dominating contributions. Traditionally, π- and σ-aromaticity are used to describe the unsaturated and saturated systems, respectively. Thus, it is rarely reported that π-aromaticity is dominated in a saturated system. Here we demonstrate that π-aromaticity could be dominating in several fully saturated four-membered rings (4MRs), supported by various aromaticity indices including ΔBL, NICS, EDDB, MCI, and AdNDP. The origin of such π-aromaticity in saturated rings could be attributed to an introduction of two additional electrons into the π-type LUMO of the parent neutral species. Our findings represent a novel approach to achieve π-aromaticity into a fully saturated system which has traditionally been dominated by σ-aromaticity.
The hydrosilylation of unsaturated carbon-carbon bonds is one of the most critical reactions in silicone industrial production. The homogeneous Speier's catalyst, Karstedt's catalyst, and other noble metal-based catalysts are widely used. However, simplifying the separation of the homogeneous catalyst from reaction products and reducing the high cost of precious metals is still challenging. This review describes the recent development of heterogeneous catalysts for alkene, alkyne, and allene hydrosilylations, which can effectively solve problems in homogeneous hydrosilylation.
Dicarboxylic acids have a wide range of applications in the polymer industry to construct valuable materials. Photocatalysis has recently emerged as an efficient and sustainable strategy to generate dicarboxylic acids. However, photocatalytic dicarboxylation with CO2 is mainly limited to unsaturated bonds, and the dicarboxylation of C–C single bonds still remains a challenge. Herein, we report a photocatalytic dicarboxylation of C–C single bonds in strained rings with CO2 units via consecutive photo-induced electron transfer (ConPET). It is also the first photocatalytic reductive ring-opening reaction of cyclobutanes. Notably, this transition-metal-free protocol exhibits good functional group tolerance, broad substrate scope, facile scalability, and easy product derivatizations. Moreover, diacids can easily be derivatized to main-chain liquid crystalline polyesters.
The over-exploitation of fossil fuel energy has brought about serious environmental problems. It would be of great significance to construct efficient energy conversion and storage system to maximize utilize renewable energy, which contributes to reducing environmental hazards. For the past few years, in terms of electrocatalysis and energy storage, carbon fiber materials show great advantages due to its outstanding electrical conductivity, good flexibility and mechanical property. As a simple and low-cost technique, electrospinning can be employed to prepare various nanofibers. It is noted that the functional fiber materials with different special structure and composition can be obtained for energy conversion and storage by combining electrospinning with other post-processing. In this paper, the structural design, controllable synthesis and multifunctional applications of electrospinning-derived functional carbon-based materials (EFCMs) is reviewed. Firstly, we briefly introduce the history, basic principle and typical equipment of electrospinning. Then we discuss the strategies for preparing EFCMs with different structures and composition in detail. In addition, we show recently the application of advanced EFCMs in energy conversion and storage, such as nitrogen species reduction reaction, CO2 reduction reaction, oxygen reduction reaction, water-splitting, supercapacitors and ion batteries. In the end, we propose some perspectives on the future development direction of EFCMs.
Molecular weaving is a powerful approach to make molecularly woven materials that have showed unprecedented characteristics and properties intrinsically distinct to those of non-woven materials. We here report a facile and efficient approach for the synthesis of 2D woven supramolecular polymers by differentiated self-assembly through orthogonal noncovalent interactions. Importantly, the difference in binding strength of two orthogonal noncovalent interactions can be used to control the process of molecular weaving. Consequently, single-layered 2D woven supramolecular polymers were synthesized and fully characterized by various techniques. This study demonstrates a controllable method for molecular weaving, and will significantly hasten the development of molecularly woven materials.
Quinoidal π-conjugated structures, a kind of fundamental subunits for organic π-systems, may produce some intriguing optical, electronic and magnetic properties of polycyclic hydrocarbons (PHs). Herein, we report two thienothiophene-centered ladder-type polycyclic molecules (1 and 2), which possess one quinoidal thienothiophene moiety and two para-quinodimethane (p-QDM) subunits, respectively. As theoretically and experimentally studied, while 1 is a fully closed-shell molecule, 2 owns an open-shell structure along with partial contribution of tetraradical state that is induced by the resonance of p-QDM. Moreover, although 2 has a larger π-conjugated skeleton and open-shell electronic state, it exhibits larger bandgap and blue-shifted absorption. On the other hand, the reversible oxidation activity of 1 enables the preparation of its dication, and the studies on its single-crystal and aromatic structures demonstrate that its two positive charges are delocalized onto the oxygen atoms, thus achieving fully π-extended structure and near-infrared absorption. This study not only gains insight into quinoidal π-subunits, but also provides an important basis for the development of antiaromatic and open-shell π-electron materials.
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